Pesticidal 1-arylpyrazoles

ABSTRACT

1-Arylpyrazoles of the formula: ##STR1## wherein R 31 , R 32 , R 33 , R 4 , R 5 , R 12 , R 13 , R 14 , R 15  and Z are as defined in the specification, are useful as pesticides or as intermediates to other pesticides. Compositions comprising the compounds of formula (I) and methods for their use, particularly in agriculture and for animal protection, as pesticides, especially for controlling arthropods, are described.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority of copending U.S. Provisionalpatent application Ser. No. 60/040,136, filed Mar. 10, 1997,incorporated by reference herein in its entirety and relied upon.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to new derivatives of 1-arylpyrazoles which havesome valuable properties either as pesticides or as intermediates tomake other pesticides. The invention further pertains to compositions ofsaid compounds and methods, using said compounds either as intermediatesto make other pesticides, or for the control of arthropod pests, inparticular to the application of said compounds or compositions inagricultural methods of use or for animal protection, particularly aspesticides, for controlling arthropods.

2. Description of the Related Art

International Patent Publication No. WO 87/03781 and European PatentPublication Nos. 0295117, 0154115, 0201852 describe insecticidal1-(substituted phenyl)pyrazoles. Other prior art is also found in thetext of these patent applications or the patents issued therefrom.

International Patent Publication Nos. WO 93/06089 and WO 94/21606 alsodescribe insecticidal 1-(4-SF₅ substituted phenyl) heterocycles whichmay be pyrroles as well as imidazoles or pyrazoles. The teaching ofthese patents is not substantially different from International PatentPublication No. WO 87/03781 or from European Patent Publication No.0295117 as far as pyrazoles are concerned.

Various pesticidal pyrazoles have been disclosed in various patents orpatent applications: European 0418016, 0403309, 0352944; U.S. Pat. Nos.5,104,994, 5,079,370, 5,047,550, 5,232,940, 4,810,720, 4,804,675,5,306,694, 4,614,533, 5,187,185, 5,223,525; WO 93/06089, 94/21606.

Due to the many existing pests and crops and conditions of attacks ofcrops by pests, there is a need for further novel pesticidal compounds.

OBJECTS AND SUMMARY OF THE INVENTION

It is an object of the present invention to provide new pesticidalcompounds of the 1-arylpyrazole family together with processes for theirpreparation.

A second object of the present invention is to provide pesticidalcompositions and pesticidal methods of use of the pesticidal pyrazolecompounds against arthropods, especially insects, particularly inagricultural or horticultural crops, forestry, veterinary medicine orlivestock husbandry, or in public health.

A third object of the present invention is to provide very activecompounds, with broad spectrum pesticidal activity, as well as compoundswith selective special activity, e.g., aphicidal, miticidal, foliarinsecticidal, soil insecticidal, systemic, antifeeding or pesticidalactivity via seed treatment.

These and other objects, which are met in whole or in part by theinstant invention, shall become readily apparent from the description ofthe invention which follows.

This invention embraces novel chemical compounds having an insecticidal,miticidal, nematocidal or anthelninthic activity.

The invention relates to compounds having the general formula (I):##STR2## wherein: R₃₁ and R₃₂ may individually be OR₂₀, S(O)_(n) R₂₀, orN(R₂₀)(R₂₁); or R₃₁ and R₃₂ may also connect to form O[C(R₂₂)(R₂₃)]_(m)O, S(O)_(n) [C(R₂₂)(R₂₃)]_(m) S(O)_(a), O(CH₂)_(m) S(O)_(n),O[C(R₂₂)(R₂₃)]_(m) (NR₂₀), S(O)_(n) [C(R₂₂)(R₂₃)]_(m) (NR₂₀), NR₂₁[C(R₂₂)(R₂₃)]_(m) NR₂₀, NR₂₁ [C(O)(CH₂)_(m) ]NR₂₀ ;

m is an integer from 1 to 5;

when m is greater than one, the groups [C(R₂₂)(R₂₃)] may be the same ordifferent;

R₂₀, R₂₁ may individually be H, alkyl, aryl, benzyl, allyl, propargyl;

R₂₂, R₂₃ may individually be H; halogen; OH; NH₂ ; COOR₂₀ ; C(O)NH₂ ;C(O)N(R₂₀)(R₂₁); C(S)NH₂ ; OC(O)N(R₂₀)(R₂₁); CN; NO₂ ; C(S)N(R₂₀)(R₂₁);alkyl which may optionally be substituted with OH, NH₂, halogen, CN,NO₂, COOR₂₀, C(O)NH₂, C(S)NH₂ ; S(O)_(b) alkyl; alkoxy; S(O)_(c) R₂₀ ;

R₄ is R₂₆ ; S(O)_(d) R₂₆ ; S(═R₂₇)(═NR₂₈)R₂₆ ;

R₂₆ is alkyl optionally substituted with one or more halogen which maybe the same or different;

R₅ is NH₂, alkylamino where the alkyl may be substituted with NO₂,halogen, CN, alkoxycarbonyl, OH, alkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl or carbamoyl; or R₅ is a radical having the formula:##STR3## wherein R₄, R₁₂, R₁₃, R₁₄, R₁₅, Z and R₃₃ are identical to R₄,R₁₂, R₁₃, R₁₄, R₁₅, Z and R₃₃, respectively, in formula (I) above;

R₂₇ is NR₂₈, O or a lone pair of electrons;

R₂₈ is selected from H; C₁ -C₆ alkyl; C₁ -C₆ haloalkyl; COR₂₄ ; S(O)_(e)R₂₄ ; COOR₂₄ ; C(O)N(R₂₀)(R₂₁); C(O)SR₂₄ ; C(S)OR₂₄ ; SO₂ NR₂₀ R₂₁ ;P(O)_(q) (R₂₀)(R₂₁); P(O)_(q) (OR₂₀)(OR₂₁); C(═NR₂₀)NR₂₀ R₂₁ ;C(═NR₂₀)(OR₂₁); C(S)N(R₂₀)(R₂₁); C(O)C(O)R₂₀ ; C(O)C(O)OR₂₀ ;C(O)C(O)NR₂₀ R₂₁ ; and C(O)NR₂₀ SO₂ R₂₁ ;

q is 0 or 1;

R₂₄ is allyl optionally substituted with NO₂, CN, halogen, alkoxy,amino, alkoxycarbonyl or OH;

Z is N or C--R₁₆ ;

R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ may individually be H; halogen; SF₅ ; CN; NO₂; R₂₅ ; S(O)_(f) R₂₅ ; OH; OR₂₅ ; N(R₃₆)(R₃₇); CON(R₂₅)(R₃₇); N₃(azido);

R₃₆ and R₃₇ may individually be H, alkyl;

R₂₅ may be alkyl optionally substituted with one or more halogen whichmay be the same or different;

R₃₃ is C₁ to C₃ alkyl, optionally substituted by one or more halogen,NO₂, alkoxy, CN, COOH, COO-alkyl, C(O)NH₂ ; and

n, a, b, c, d, e and f, which are the same or different, are each 0, 1or 2; and pesticidally acceptable salts thereof.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

The stereoisomers, e.g. diastereomers and optical isomers, having theformula (I) are included in the invention as well.

In this description, the term `alkyl` when unqualified generally means astraight- or branched-chain alkyl having from one to six carbon atoms.The term `aryl` means C₆ -C₁₀ aryl, e.g. phenyl or naphthyl, optionallybearing one or more substituents selected from the group consisting ofhalogen, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, CN, NO₂, C₁ -C₆ haloalkyl and C₁-C₆ haloalkoxy.

Preferred compounds of formula (I) include those wherein R₁₃ and R₁₅ areH or halogen; R₁₂ is halogen; R₁₆ is H or halogen; and/or R₁₄ ishalogen, SF5, R₂₅, S(O)_(f) R₂₅ or OR₂₅. Compounds in which R₁₂ ischlorine, R₁₃ and R₁₅ are H, R₁₄ is CF₃, and Z is C--Cl, are especiallypreferred.

Compounds of formula (I) wherein R₄ is S(O)_(d) R₂₆ and Z is C--R₁₆ arealso preferred.

The symbol m is preferably 2, 3 or 4, more preferably 2 or 3, mostpreferably 2.

Other preferred compounds of formula (I) are those wherein:

R₂₆ is CH₃ or CH₂ CH₃ ; Z is C--R₁₆ ; R₁₃ and R₁₅ are H; R₁₂ is halogen;R₁₆ is H or halogen; R₁₄ is CF₃, OCF₃ or SF₅ ; and/or R₃₃ is CH₃.

Still most preferred compounds of formula (1) are those wherein:

R₃₁ and R₃₂ may individually be OCH₃ ; OC₂ H₅ ; SCH₃ ; SC₂ H₅ ; R₃₁ andR₃₂ may also connect to form OCH₂ CH₂ O; O(CH₂)₃ O; S(CH₂)₂ S;S(O)(CH₂)₂ S; S(O)(CH₂)₂ S(O); S(O)₂ (CH₂)₂ S(O); S(O)₂ (CH₂)₂ S(O)₂ ;S(CH₂)₂ O; S(O)(CH₂)₂ O; S(O)₂ (CH₂)₂ O; O(CH₂)[CH(CH₂ OH)]O;O(CH₂)[C(CH₂ OH)(CH₂ OH)]O; OCH(COOCH₃)CH(COOCH₃)O; OCH(COOC₂H₅)CH(COOC₂ H₅)O; OCH₂ C(COOCH₃)(COOCH₃)CH₂ O; OCH₂ C(COOC₂ H₅)(COOC₂H₅)CH₂ O; OCH₂ CH(CH₃)O; SCH₂ CH₂ NH; OCH₂ CH(CH₂ CH₂ OH)O; OCH₂ C(CH₂OH)₂ CH₂ O; OCH₂ CH(CH₂ SCH₃)O; or OCH₂ CH(CH₂ SOCH₃)O; particularlywhen R₄ is S(O)_(d) R₂₆ ; R₂₆ is CH₃ or CH₂ CH₃ ; Z is C--R₁₆ ; R₁₃ andR₁₅ are H; R₁₂ is halogen; R₁₆ is H or halogen; R₁₄ is CF₃, OCF₃ or SF₅; and R₃₃ is CH₃.

Preferably, the compounds of formula (I) have one or more of thefollowing features:

R₁₂ is halogen;

X is C--Cl;

R₁₃ and R₁₅ are H;

R₁₄ is CF₃ or SF₅ ;

R₅ is NH₂, CH₃ NH, or CH₃ CH₂ NH;

R₄ is CH₃ S(O), CH₃ S(O)₂ or CH₃ S;

R₃₁ and R₃₂ are OCH₃ or connect to form OCH₂ CH₂ O; OCH₂ CH(CH₃)O;S(CH₂)₂ S; S(O)(CH₂)₂ S; S(O)(CH₂)₂ S(O); S(O)₂ (CH₂)₂ S(O)₂ ;O(CH₂)[CH(CH₂ OH)]O; SCH₂ CH₂ NH; O(CH₂)CH(CH₂ SCH₃)O; O(CH₂)CH(CH₂SOCH₃).

Compounds of the general formula (I) can be prepared by reacting thecompounds of the general formula (II): ##STR4##

wherein R₄, R₅, R₁₂, R₁₃, R₁₄, R₁₅, Z and R₃₃ are as defined above andR₃₄ is oxygen or sulfur, with a compound (III) having at least onereactive functional group selected from the group consisting of alcohol,thiol, primary amine and secondary amine.

More precisely, the compound (III) may be:

an alcohol of general formula of R₂₀ OH;

a thiol of general formula of R₂₀ SH;

an amine of general formula of HN(R₂₀)(R₂₁);

or a compound of the formula

HO[C(R₂₂)(R₂₃)]_(m) OH, HS[C(R₂₂)(R₂₃)]_(m) SH, HO[C(R₂₂)(R₂₃)]_(m) SH,HO[C(R₂₂)(R₂₃)]_(m) N(R₂₀)H, HS[C(R₂₂)(R₂₃)]_(m) N(R₂₀)H, or NHR₂₀[C(R₂₂)(R₂₃)]_(m) NHR₂₁ where R₂₂ and R₂₃ may be the same or differentand R₂₀ and R₂₁ may be the same or different.

The reaction of the compound of (II) with the compound of (III) can beachieved by directly reacting the compounds of formula (II) and thecompounds (III) in a liquid medium at a temperature in the range fromabout -35° C. to about 250° C., preferably from about -10° C. to about150° C. Removal of water is preferred. The liquid medium can be achievedeither by means of the reactant or with a solvent. Possible solvents forthe reaction may be organic solvents including alcohols such asmethanol, ethanol, isopropanol; ethers such as diethyl ether,tetrahydrofuran, dioxane, dimethoxyethane; nitrites such asacetonitrile; aromatic solvents such as toluene, benzene, chlorobenzene;haloalkanes such as chloroform, methylene chloride; amides such asdimethylamide; ketones such as acetone, methylisobutylketone; esterssuch as ethyl acetate. The amount of reactant is generally between about50% and about 200% what is required by the reaction (except when areactant is used as solvent, and then the amount of reactant is muchhigher). The reaction can be conducted with or without presence of acidcatalyst. The acid catalyst can be an inorganic acid such ashydrochloric acid, sulfuric acid; an organic acid such as acetic acid,formic acid, p-toluenesulfonic acid; Lewis acids such as iron (III)chloride, ammonium chloride, boron trifluoride, aluminum chloride, zinciodide, zinc chloride; acidic ion-exchange resin; clays such asMontmorillonite.

In the process described in the preceding paragraph, when R₅ is -NH₂ andR₃₄ is oxygen in the starting material of formula (II), in addition toforming a compound of formula (I) in which R₅ is -NH₂, there can beproduced, by reaction with another molecule of the starting material offormula (II), a compound of formula (I) in which R₅ is a radical offormula (Ia) set forth hereinabove. Both products are active aspesticides.

The sulfoxide and sulfone compounds of the formula (I), i.e. thecompounds in which n, a, b, c, d, e or f is 1 or 2, can also be preparedby oxidation of the corresponding sulfide using appropriate oxidationreagents including but not limited to peroxide, such as hydrogenperoxide, t-butyl peroxide; peracids such as metachloroperbenzoic acid;acyl nitrates such as acetyl nitrate and other nonperoxide agents suchas sodium periodate, sodium perborate, manganese oxide, potassiumpermanganate, N-bromosuccinimide, preferably hydrogen peroxide andsodium periodate.

In cases, such as in oxyketal sulfide, where mild conditions arerequired sodium periodate is the preferred sulfoxidation agent.

The following non-limiting Examples illustrate the invention.

EXAMPLE 1 Preparation of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-[(1,1-dimethoxy)ethyl]-4-methylthio-1H-pyrazole

A mixture of 2.0 g (0.0052 mole) of3-acetyl-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-1H-pyrazole,1.7 ml (0.0156 mole) of trimethyl orthoformate, 0.060 g (0.0003 mole) ofpara-toluenesulfonic acid monohydrate and 10 ml of methanol was heatedat 40° C. for about 8 hours, then left 64 h at 20° C. The mixture wasmixed with a saturated solution of NaHCO₃, extracted withdichloromethane, and successively dried, filtered, evaporated,chromatographed on silica gel. 0.59 g of the title compound having amelting point of about 149° C. was obtained.

EXAMPLE 2 Preparation of5-amino-1-[(2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,3-dioxolane-2-yl)-4-methylthio-1H-pyrazole

A mixture of 10.0 g (26.03 mmol) of[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-acetyl-4-methylthio-1H-pyrazole,1.94 g (31.23 mmol) of 1,2-ethanediol, 0.49 g (2.6 mmol) ofp-toluenesulfonic acid and 500 ml of benzene was heated to reflux withremoval of water for 10 hr. The mixture was mixed with aqueous sodiumbicarbonate. The organic layer was washed with saturated aqueouspotassium chloride and then successively dried, evaporated,chromatographed. 2.33 g of the title compound was obtained (meltingpoint about 143° C.).

EXAMPLE 3 Preparation of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,3-dioxolane-2-yl)-4-methylsulfinyl-1H-pyrazole

To a solution of 244 microliters of 0.5 M sodium periodate in 2.5 ml ofmethanol at 0° C. was added 500 mg of the product of EXAMPLE 2. Themixture was stirred at 0° C. for 20 min and then left for 10 hours at20° C. The mixture was successively extracted with methylene chlorideand water, separated, dried, evaporated so as to give the titlecompound; mass spectral analysis gave M+H=444 (Molecular weight=443).

EXAMPLE 4 Preparation of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,3-dithiolane-2-yl)-4-methylthio-1H-pyrazole

A mixture of 1 g (2.60 mmol) of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-acetyl-4-methylthio-1H-pyrazole,0.26 ml (3.10 mmol) of 1,2-ethanedithiol, 0.084 g (0.5 mmol) ofiron(III) chloride and 25 ml of methylene chloride was stirred at 20° C.under an inert atmosphere for 6 days. The mixture was evaporated andchromatographed so as to give 100 mg of yellow oil of the titlecompound. Mass spectral analysis gave a molecular weight of 460.

EXAMPLE 5 Preparation of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methylthiazolidine-2-yl)-4-methylsulfinyl-1H-pyrazole

A mixture of 1 g (2.5 mmol) of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-acetyl-4-methylsulfinyl-1H-pyrazole,0.284 g (2.5 mmol) of 2-aminoethanethiol hydrochloride, 348 microliters(2.50 mmol) of triethylamine, 50 mg of p-toluenesulfonic acid and 30 mlof benzene was heated to reflux with removal of water overnight. Themixture was successively cooled, filtered, evaporated, chromatographedso as to give 20 mg of the title compound as white solid; melting point85° C.

EXAMPLE 6 Preparation of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,3-oxathiolane-2-yl)-4-methylsulfonyl-1H-pyrazole

To a stirred solution of 54.34 grams (0.131 mole) of3-acetyl-5-amino-1-[2,6-dichloro-4-(trifluromethyl)phenyl]-4-methylsulfonyl-1H-pyrazolein 500 mL of dioxane was added, in sequence, 36.7 mL (0.522 mole) ofmercaptoethanol, 71.1 grams (0.522 mole) of anhydrous zinc chloride and62.1 grams (0.522 mole) of anhydrous sodium sulfate while cooling at 0°C. in an ice bath. The mixture was then stirred for a period ofapproximately 17 hours while allowing it to warm to room temperature.The mixture was filtered to remove salts and the filtrate concentratedunder reduced pressure and diluted with 40 mL of acetonitrile,collecting the product by filtering at 35° C. The filtrate was furtherdiluted with acetonitrile to obtain a second crop of product. Thecombined crops of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,3-oxathiolane-2-yl)-4-methylsulfonyl-1H-pyrazolegave 30.53 grams of material, having a melting point of 201° C. Thiscompound is hereinafter referred to as Compound No. 23.

EXAMPLE 7 Preparation of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,1,3,3-tetraoxo-1,3-dithiolane-2-yl)-4-methylsulfonyl-1H-pyrazole

To an ice-cooled solution of 0.49 gram (0.00096 mole) of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1-oxo-1,3-dithiolane-2-yl)-4-methylsulfonyl-1H-pyrazolein 4 mL of trifluoroacetic acid was added 0.4 mL (0.004 mole) of 30%hydrogen peroxide, dropwise, and the mixture stirred while allowing itto warm to room temperature for an approximate 17-hour period. Themixture was partitioned between ethyl acetate and water and the organicphase separated, washed with saturated aqueous sodium bicarbonate, thenbrine, and dried over sodium sulfate. The solution was filtered,concentrated under reduced pressure, and chromatographed on silica gelto give 0.14 gram of5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-(2-methyl-1,1,3,3-tetraoxo-1,3-dithiolane-2-yl)-4-methylsulfonyl-1H-pyrazoleas a cream colored powder having a melting point of 231° C. Thiscompound is hereinafter referred to as Compound No. 25.

EXAMPLE 8 Preparation of1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-3-(4-hydroxymethyl-2-methyl-1,3-dioxolan-2-yl)-5-N-1-[[[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-1H-pyrazol-3-yl]ethylidene]amino-1H-pyrazole

In the synthesis of Compound No. 6, Table 1, by the condensation of3-acetyl-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-1H-pyrazolewith glycerol, employing the procedure of Example 2, above, working upthe reaction mixture resulted in isolation of1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-3-(4-hydroxymethyl-2-methyl-1,3-dioxolan-2-yl)-5-N-1-[[[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-1H-pyrazol-3-yl]ethylidene]amino-1H-pyrazoleas a by-product having a melting point of 100° C. This compound isreferred to hereinafter as Compound No. 9.

The following compounds were prepared according one of the processesdescribed in the Examples 1 to 8:

    ______________________________________                                          #STR5##                                                                     Compound   R.sub.31                                                                              R.sub.32   d   melting point                               ______________________________________                                          1 OCH.sub.3 OCH.sub.3 0 149                                                   2 OCH.sub.3 OCH.sub.3 1 153                                                 ______________________________________                                    

    ______________________________________                                          #STR6##                                                                     Compound                                                                              R.sub.310                                                                             R.sub.320                                                                             R.sub.17 d   melting point                            ______________________________________                                         3      O       O       H        0   100                                         4 O O CH.sub.3 0 126                                                          5 O O H 2 194                                                                 6 O O CH.sub.2 OH 0  71                                                       7 O O CH.sub.2 OH 2 183                                                       8 O O CH.sub.3 2 202                                                         10 O O H 1  68                                                                11 O O CH.sub.3 1  90                                                         15 S NH H 1  85                                                               16 S S H 0 (M + H).sup.+  = 460                                               17 S S H 2 207                                                                18 S S H 1 127                                                                19 SO S H 0   179.5                                                           20 SO S H 1 182                                                               21 SO S H 2 195                                                               22 SO SO H 2 175                                                              23 S O H 2 201                                                                24 S O H 0 (M + H)+ = 444                                                     25 SO.sub.2 SO.sub.2 H 2 231                                                  26 O O CH.sub.2 OH 1 153                                                      27 O O CH.sub.2 SCH.sub.3 0  43                                               28 O O CH.sub.2 SOCH.sub.3 0  68                                              29 O O CH.sub.2 SOCH.sub.3 1  82                                              30 O O CH.sub.2 SCH.sub.3 2  68                                               31 O O CH.sub.2 SOCH.sub.3 2 110                                            ______________________________________                                    

    ______________________________________                                          #STR7##                                                                     Compound   R.sub.5     d     Melting Point                                    ______________________________________                                        34         EtNH        2     119                                                35 MeNH 2 188                                                                 36 EtNH 0 (M + H).sup.+  = 456                                                37 EtNH 1 (M + H).sup.+  = 472                                                38 MeNH 0 (M + H).sup.+  = 442                                                39 MeNH 1 (M + H).sup.+  = 458                                              ______________________________________                                    

    ______________________________________                                          #STR8##                                                                     Compound 9                                                                       -                                                                            #STR9##                                                                        -                                                                          Compd   R.sub.310                                                                            R.sub.320                                                                              R.sub.17                                                                            R.sub.18                                                                              d   M.P.                                ______________________________________                                          12 O O H H 0 143                                                              13 O O H H 2 223                                                              14 O O CH.sub.2 OH CH.sub.2 OH 0  85                                        ______________________________________                                    

The present invention further provides a method of control of pests at alocus which comprises the treatment of the locus (e.g., by applicationor administration) with an effective amount of a compound of formula (I)or a pesticidally acceptable salt thereof, wherein the substituentgroups are as hereinbefore defined. The locus includes, for example, thepest itself or the place (plant, animal, field, structure, premises,forest, orchard, waterway, soil, plant or animal product, or the like)where the pest resides or feeds.

In particular, the present invention provides a method for the systemiccontrol of arthropods at a locus, especially some insects or mites whichfeed on the above-ground portions of plants. Control of such foliarpests may be provided by direct foliar application or by application by,for example, soil spray or granule application to the plant roots orplant seeds with subsequent systemic translocation to the above-groundportions of the plants. Such systemic activity includes the control ofinsects which reside not only at the point of application but at aremote part of the plant, for example, by translocation from one side ofa leaf to the other or from a treated leaf to an untreated leaf.Examples of the classes of insect pests which may be systemicallycontrolled by the compounds of the invention include the Homoptera order(piercing-sucking), Hemiptera order (piercing-sucking), and Thysanopteraorder. The invention is especially appropriate for aphids and thrips.

As is evident from the foregoing pesticidal uses, the present inventionprovides pesticidally active compounds and methods of use of saidcompounds for the control of a number of pest species which includes:arthropods, especially insects or mites; plant nematodes; or helminth orprotozoan pests. The compounds of formula (I) or pesticidally acceptablesalts thereof thus are advantageously employed in practical uses, forexample, in agricultural or horticultural crops, forestry, veterinarymedicine or livestock husbandry, or in public health. From this pointforward, whenever the term "compounds of formula (I)" is used this termembraces compounds of formula (I) and their pesticidally acceptablesalts. The term "compound of formula (I)" embraces a compound of formula(I) and a pesticidally acceptable salt thereof.

The compounds of this invention may in addition be used to control soilinsects, such as corn rootworm, termites (especially for protection ofstructures), root maggots, wireworms, root weevils, stalkborers,cutworms, root aphids, or grubs. They may also be used to provideactivity against plant pathogenic nematodes, such as root-knot, cyst,dagger, lesion, or stem or bulb nematodes, or against mites. For thecontrol of soil pests, for example corn rootworm, the compounds areadvantageously applied to or incorporated at an effective rate into thesoil in which crops are planted or to be planted or to the seeds orgrowing plant roots.

In the area of public health, the compounds are especially useful in thecontrol of many insects, especially filth flies or other Dipteran pests,such as houseflies, stableflies, soldierflies, hornflies, deerflies,horseflies, midges, punkies, blackflies, or mosquitoes.

Compounds of the invention may be used in the following applications andon the following pests including arthropods, especially insects ormites, nematodes, or helminth or protozoan pests:

In the protection of stored products, for example cereals, includinggrain or flour, groundnuts, animal feedstuffs, timber or householdgoods, e.g. carpets and textiles, compounds of the invention are usefulagainst attack by arthropods, more especially beetles, includingweevils, moths or mites, for example Ephestia spp. (flour moths),Anthrenus spp. (carpet beetles), Tribolium spp. (flour beetles),Sitophilus spp. (grain weevils) or Acarus spp. (mites).

In the control of cockroaches, ants or termites or similar arthropodpests in infested domestic or industrial premises or in the control ofmosquito larvae in waterways, wells, reservoirs or other running orstanding water.

For the treatment of foundations, structures or soil in the preventionof the attack on building by termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

In agriculture against adults, larvae and eggs of Lepidoptera(butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens(tobacco budworm), Heliothis armigera and Heliothis zea. Against adultsand larvae of Coleoptera (beetles) e.g. Anthonomus spp. e.g. grandis(cotton boll weevil), Leptinotarsa decemlineata (Colorado potatobeetle), Diabrotica spp. (corn rootworms). Against Heteroptera(Hemiptera and Homoptera) e.g. Psylla spp., Bemisia spp., Trialeurodesspp., Aphis spp., Myzus spp., Megoura viciae, Phylloxera spp.,Nephotettix spp. (rice leaf hoppers), Nilaparvata spp.

Against Diptera e.g. Musca spp. Against Thysanoptera such as Thripstabaci. Against Orthoptera such as Locusta and Schistocerca spp.(locusts and crickets) e.g. Gryllus spp., and Acheta spp. for example,Blatta orientalis, Periplaneta americana, Blatella germanica, Locustamigratoria migratorioides, and Schistocerca gregaria. Against Collembolae.g. Periplaneta spp. and Blattela spp. (roaches). Against Isoptera e.g.Coptotermes spp. (termites).

Against arthropods of agricultural significance such as Acari (mites)e.g. Tetranychus spp., and Panonychus spp.

Against nematodes which attack plants or trees of importance toagriculture, forestry or horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants, forexample root-knot nematodes such as Meloidogyne spp. (e.g. M incognita).

In the field of veterinary medicine or livestock husbandry or in themaintenance of public health against arthropods, helminths or protozoawhich are parasitic internally or externally upon vertebrates,particularly warm-blooded vertebrates, for example domestic animals,e.g. cattle, sheep, goats, equines, swine, poultry, dogs or cats, forexample Acarina, including ticks e.g. Ixodes spp., Boophilus spp. e.g.Boophilus microplus, Rhipicephalus spp. e.g. Rhipicephalusappendiculatus, Ornithodorus spp. (e.g. Ornithodorus moubata) and mites(e.g. Damalinia spp.); Diptera (e.g. Aedes spp., Anopheles spp., Muscaspp., Hypoderma spp.); Hemiptera.; Dictyoptera (e.g. Periplaneta spp.,Blatella spp.); Hymenoptera; for example against infections of thegastro-intestinal tract caused by parasitic nematode worms, for examplemembers of the family Trichostrongylidae; in the control and treatmentof protozoal diseases caused by, for example, Eimeria spp. e.g.Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp.,Trichomonadidae spp., Toxoplasma spp. and Theileria spp.

In practical use for the control of arthropods, especially insects ormites, or nematode pests of plants, a method, for example, comprisesapplying to the plants or to the medium in which they grow an effectiveamount of a compound of the invention. For such a method, the activecompound is generally applied to the locus in which the arthropod ornematode infestation is to be controlled at an effective rate in therange of about 5 g to about 1 kg of the active compound per hectare oflocus treated. Under ideal conditions, depending on the pest to becontrolled, a lower rate may offer adequate protection. On the otherhand, adverse weather conditions, resistance of the pest or otherfactors may require that the active ingredient be used at higher rates.The optimum rate depends usually upon a number of factors, for example,the type of pest being controlled, the type or the growth stage of theinfested plant, the row spacing or also the method of application. Morepreferably an effective rate range of the active compound is from about50 g/ha to about 400 g/ha.

When a pest is soil-borne, the active compound, generally in aformulated composition, is distributed evenly over the area to betreated (ie, for example broadcast or band treatment) in any convenientmanner and is applied at rates from about 5 g to about 1 kg ai/ha,preferably from about 50 to about 250 g ai/ha. When applied as a rootdip to seedlings or drip irrigation to plants, the liquid solution orsuspension contains from about 0.075 to about 1000 mg ai/l, preferablyfrom about 25 to about 200 mg ai/l. Application may be made, if desired,to the field or crop-growing area generally or in close proximity to theseed or plant to be protected from attack. The active component can bewashed into the soil by spraying with water over the area or can be leftto the natural action of rainfall. During or after application, theformulated compound can, if desired, be distributed mechanically in thesoil, for example by ploughing, disking, or use of drag chains.Application can be prior to planting, at planting, after planting butbefore sprouting has taken place, or after sprouting.

The compounds of the invention and methods of control of pests therewithare of particular value in the protection of field, forage, plantation,glasshouse, orchard or vineyard crops, of ornamentals, or of plantationor forest trees, for example: cereals (such as wheat or rice), cotton,vegetables (such as peppers), field crops (such as sugar beets, soybeansor oil seed rape), grassland or forage crops (such as maize or sorghum),orchards or groves (such as of stone or pit fruit or citrus), ornamentalplants, flowers or vegetables or shrubs under glass or in gardens orparks, or forest trees (both deciduous and evergreen) in forests,plantations or nurseries.

They are also valuable in the protection of timber (standing, felled,converted, stored or structural) from attack, for example, by sawfliesor beetles or termites.

They have applications in the protection of stored products such asgrains, fruits, nuts, spices or tobacco, whether whole, milled orcompounded into products, from moth, beetle, mite or grain weevilattack. Also protected are stored animal products such as skins, hair,wool or feathers in natural or converted form (e.g. as carpets ortextiles) from moth or beetle attack as well as stored meat, fish orgrains from beetle, mite or fly attack.

Additionally, the compounds of the invention and methods of use thereofare of particular value in the control of arthropods, helminths orprotozoa which are injurious to, or spread or act as vectors of diseasesin domestic animals, for example those hereinbefore mentioned, and moreespecially in the control of ticks, mites, lice, fleas, midges, orbiting, nuisance or myiasis flies. The compounds of the invention areparticularly useful in controlling arthropods, helminths or protozoawhich are present inside domestic host animals or which feed in or onthe skin or suck the blood of the animal, for which purpose they may beadministered orally, parenterally, percutaneously or topically.

Furthermore, compounds of the invention may be useful for coccidiosis, adisease caused by infections from protozoan parasites of the genusEimeria. It is an important potential cause of economic loss in domesticanimals and birds, particularly those raised or kept under intensiveconditions. For example, cattle, sheep, pigs or rabbits may be affected,but the disease is especially important in poultry, particularly inchickens. Administration of a small amount of a compound of theinvention, preferably by a combination with feed is effective inpreventing or greatly reducing the incidence of coccidiosis. Thecompounds are effective against both the cecal form and the intestinalforms. Furthermore, the compounds of the invention may also exert aninhibiting effect on oocytes by greatly reducing the number andsporulation of those produced. The poultry disease is generally spreadby the birds picking up the infectious organism in droppings in or oncontaminated litter, ground, food, or drinking water. The disease ismanifested by hemorrhage, accumulation of blood in the ceca, passage ofblood to the droppings, weakness and digestive disturbances. The diseaseoften terminates in the death of the animal, but the fowl which survivesevere infections have had their market value substantially reduced as aresult of the infection.

The compositions hereinafter described for application to growing cropsor crop growing loci or as a seed dressing may, in general,alternatively be employed for topical application to animals or in theprotection of stored products, household goods, property or areas of thegeneral environment. Suitable means of applying the compounds of theinvention include:

to growing crops as foliar sprays, dusts, granules, fogs or foams oralso as suspensions of finely divided or encapsulated compositions assoil or root treatments by liquid drenches, dusts, granules, smokes orfoams; to seeds of crops via application as seed dressings by liquidslurries or dusts;

to animals infested by or exposed to infestation by arthropods,helminths or protozoa, by parenteral, oral or topical application ofcompositions in which the active ingredient exhibits an immediate and/orprolonged action over a period of time against the arthropods, helminthsor protozoa, for example by incorporation in feed or suitableorally-ingestible pharmaceutical formulations, edible baits, salt licks,dietary supplements, pour-on formulations, sprays, baths, dips, showers,jets, dusts, greases, shampoos, creams, wax smears or livestockself-treatment systems;

to the environment in general or to specific locations where pests maylurk, including stored products, timber, household goods, or domestic orindustrial premises, as sprays, fogs, dusts, smokes, wax-smears,lacquers, granules or baits, or in tricklefeeds to waterways, wells,reservoirs or other running or standing water;

to domestic animals in feed to control fly larvae feeding in theirfeces.

The following non-limiting examples illustrate the use of the compoundsof the invention in controlling pests.

The species tested were as follows:

    ______________________________________                                        GENUS, SPECIES      COMMON NAME                                               ______________________________________                                        Aphis gossypii      cotton leaf aphid                                           Musca domestica housefly                                                      Diabrotica virgifera Western cornrootworm                                     Periplaneta americana American Cockroaches                                    Spodoptera eridania Southern armyworm                                         Schizaphis graminum greenbug                                                  Ctenocephalides felis Cat flea                                                Rhipicephalus sanguineus Brown dog tick                                     ______________________________________                                    

The Soil Drench Test (Systemic Activity)

Cotton and sorghum plants were established in pots. One day prior totreatment, each pot was infested with about 25 aphids of a mixedpopulation. Cotton plants were infested with aphids and sorghum plantswere infested with the greenbug. The selected compound of formula (I)was applied to the soil surface in a dilution that delivered theequivalent of 10.0 ppm soil concentration by weight. Aphid counts wereobtained at 5 DAT (=days after treatment). The number of aphids on thetreated plants was compared to the number of those on the untreatedcontrol plants. This test shows systemic activity (migration of theactive ingredient).

The Housefly Bait/Contact Test

About 25 four to six-day-old adult houseflies were anesthetized andplaced in a cage with a sugar water bait solution containing thecompound. The concentration of the selected compound of formula (I) inthe bait solution was 50 ppm. After 24 hours, flies which showed nomovement on stimulation were considered dead.

Foliar Application (Contact Test) with Aphids

Aphid-infested cotton plants were placed on a revolving turntable, andsprayed to runoff with a 100 ppm formulation of the selected compound offormula (I). The treated, A. gossypii-infested plants were held forthree days after treatment, after which the dead aphids were counted.

The obtained results are as follows. In the table that follows `X` meanshighly active; `+` means moderately active; and `-` means low activity.

    ______________________________________                                              Systemic  Systemic Activity on                                            Compd. activity on activity on house flies by Foliar activity on                                                No. aphids greenbugs contact aphids       ______________________________________                                         1    X         X        X         +                                             2 + X X X                                                                     3 X X X X                                                                     4 X X X X                                                                     5 X X X X                                                                     6 + X - -                                                                     7 X X + X                                                                     8 X X X X                                                                     9 - - X -                                                                    10 X X X X                                                                    11 X X X X                                                                    12 X X X X                                                                    13  X X X                                                                     14 -  - -                                                                     15 X X X -                                                                    16 - X X +                                                                    17 X X X +                                                                    18 - + X X                                                                    19 - + X X                                                                    20 - - X -                                                                    21 - - X -                                                                    22 X + - -                                                                    23 X  -                                                                       24 X X                                                                        25 -  -                                                                       26 - + X -                                                                    27 X + X -                                                                    28 X - X X                                                                    29 X - X X                                                                    30 X  -                                                                       31 X  + +                                                                     32 X X X X                                                                    33 - - - -                                                                    34 X X X X                                                                    35 X X X X                                                                    36 X  X +                                                                     37 X  X X                                                                     38 X X X                                                                      39 + X -                                                                    ______________________________________                                    

In practice, the compounds of the invention most frequently form partsof compositions. The invention therefore also relates to a pesticidalcomposition comprising a compound of formula (I) or a pesticidallyacceptable salt thereof, and a pesticidally acceptable carrier. Thesecompositions can be employed to control: arthopods, especially insectsor mites; nematodes; or helminth or protozoan pests. The compositionsmay be of any type known in the art suitable for application to thedesired pest in any premises or indoor or outdoor area or by internal orexternal administration to vertebrates. These compositions contain atleast one compound of formula (I) or a pesticidally acceptable saltthereof, such as described earlier, as the active ingredient incombination or association with one or more other compatible componentswhich are, for example, solid or liquid carriers or diluents, adjuvants,surface-active agents, or the like appropriate for the intended use andwhich are agronomically or medicinally acceptable. These compositions,which may be prepared by any manner known in the art, likewise form apart of this invention.

These compositions may also contain other kinds of ingredients such asprotective colloids, adhesives, thickeners, thixotropic agents,penetrating agents, spray oils (especially for acaricidal use),stabilizers, preservative agents (especially mold preservatives),sequestering agents, or the like, as well as other known activeingredients with pesticidal properties (particularly insecticidal,miticidal, nematicidal, or fungicidal) or with properties regulating thegrowth of plants. More generally, the compounds employed in theinvention may be combined with all the solid or liquid additivescorresponding to the usual techniques of formulation.

Compositions, suitable for applications in agriculture, horticulture, orthe like include formulations suitable for use as, for example, sprays,dusts, granules, fogs, foams, emulsions, or the like.

The effective use doses of the compounds employed in the invention canvary within wide limits, particularly depending on the nature of thepest to be eliminated or degree of infestation, for example, of cropswith these pests. In general, the compositions according to theinvention preferably contain, particularly for use in agriculture, about0.05 to about 95% (by weight) of a compound of formula (I) or apesticidally acceptable salt thereof according to the invention, about 1to about 95% of one or more solid or liquid carriers and, optionally,about 0.1 to about 50% of one or more other compatible components, suchas surface-active agents or the like.

In the present account, the term "carrier" denotes an organic orinorganic ingredient, natural or synthetic, with which the activeingredient is combined to facilitate its application, for example, tothe plant, to seeds or to the soil. This carrier is therefore generallyinert and it must be acceptable (for example, agronomically acceptable,particularly to the treated plant).

The carrier may be a solid, for example, clays, natural or syntheticsilicates, silica, resins, waxes, solid fertilizers (for exampleammonium salts), ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceousearth, or ground synthetic minerals, such as silica, alumina, orsilicates especially aluminum or magnesium silicates. As solid carriersfor granules the following are suitable: crushed or fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite; syntheticgranules of inorganic or organic meals; granules of organic materialsuch as sawdust, coconut shells, corn cobs, corn husks or tobaccostalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbentcarbon black; water soluble polymers, resins, waxes; or solidfertilizers. Such solid compositions may, if desired, contain one ormore compatible wetting, dispersing, emulsifying or coloring agentswhich, when solid, may also serve as a diluent.

The carrier may also be liquid, for example: water; alcohols,particularly butanol or glycol, as well as their ethers or esters,particularly methylglycol acetate; ketones, particularly acetone,cyclohexanone, methylethyl ketone, methylisobutylketone, or isophorone;petroleum fractions such as paraffinic or aromatic hydrocarbons,particularly xylenes or alkyl naphthalenes; mineral or vegetable oils;aliphatic chlorinated hydrocarbons, particularly trichloroethane ormethylene chloride; aromatic chlorinated hydrocarbons, particularlychlorobenzenes; water-soluble or strongly polar solvents such asdimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; liquefiedgases; or the like or a mixture thereof.

The surface-active agent may be an emulsifying agent, dispersing agentor wetting agent of the ionic or non-ionic type or a mixture of suchsurface-active agents. Among these are e.g., salts of polyacrylic acids,salts of lignosulfonic acids, salts of phenolsulfonic ornaphthalenesulfonic acids, polycondensates of ethylene oxide with fattyalcohols or fatty acids or fatty esters or fatty amines, substitutedphenols (particularly alkylphenols or arylphenols), salts ofsulfosuccinic acid esters, taurine derivatives (particularlyalkyltaurates), phosphoric esters of alcohols or of polycondensates ofethylene oxide with phenols, esters of fatty acids with polyols, orsulfate, sulfonate or phosphate functional derivatives of the abovecompounds. The presence of at least one surface-active agent isgenerally essential when the active ingredient and/or the inert carrierare only slightly water soluble or are not water soluble and the carrieragent of the composition for application is water.

Compositions of the invention may further contain other additives suchas adhesives or colorants. Adhesives such as carboxymethylcellulose ornatural or synthetic polymers in the form of powders, granules orlattices, such as arabic gum, polyvinyl alcohol or polyvinyl acetate,natural phospholipids, such as cephalins or lecithins, or syntheticphospholipids can be used in the formulations. It is possible to usecolorants such as inorganic pigments, for example: iron oxides, titaniumoxides or Prussian Blue; organic dyestuffs, such as alizarin dyestuffs,azo dyestuffs or metal phthalocyanine dyestuffs; or trace nutrients suchas salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

Compositions containing compounds of formula (I), or pesticidallyacceptable salts thereof, which may be applied to control arthropod,plant nematode, helminth or protozoan pests, may also contain synergists(e.g. piperonyl butoxide or sesamex), stabilizing substances, otherinsecticides, acaricides, plant nematocides, anthelmintics oranticoccidials, fungicides (agricultural or veterinary as appropriate,e.g. benomyl and iprodione), bactericides, arthropod or vertebrateattractants or repellents or pheromones, deodorants, flavoring agents,dyes, or auxiliary therapeutic agents, e.g. trace elements. These may bedesigned to improve potency, persistence, safety, uptake where desired,spectrum of pests controlled or to enable the composition to performother useful functions in the same animal or area treated.

Examples of other pesticidally-active compounds which may be includedin, or used in conjunction with the compositions of the presentinvention are: acephate, chlorpyrifos, demeton-S-methyl, disulfoton,ethoprofos, fenitrothion, fenamiphos, fonofos, isazophos, isofenphos,malathion, monocrotophos, parathion, phorate, phosalone,pirimiphos-methyl, terbufos, triazophos, cyfluthrin, cypermethrin,deltamethrin, fenpropathrin, fenvalerate, permethrin, tefluthrin,aldicarb, carbosulfan, methomyl, oxamyl, pirimicarb, bendiocarb,teflubenzuron, dicofol, endosulfan, lindane, benzoximate, cartap,cyhexatin, tetradifon, avermectins, ivermectins, milbemycins,thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole.

For their agricultural application, the compounds of the formula (I), orpesticidally acceptable salts thereof, are therefore generally in theform of compositions, which are in various solid or liquid forms.

Solid forms of compositions which can be used are dusting powders (witha content of the compound of formula (I), or a pesticidally acceptablesalt thereof, ranging up to 80%), wettable powders or granules(including water dispersible granules), particularly those obtained byextrusion, compacting, impregnation of a granular carrier, orgranulation starting from a powder (the content of the compound offormula (I), or a pesticidally acceptable salt thereof, in thesewettable powders or granules being between about 0.5 and about 80%).Solid homogeneous or heterogeneous compositions containing one or morecompounds of formula (I), or pesticidally acceptable salts thereof, forexample granules, pellets, briquettes or capsules, may be used to treatstanding or running water over a period of time. A similar effect may beachieved using trickle or intermittent feeds of water dispersibleconcentrates as described herein.

Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions, or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

Liquid compositions, for example, in the form of emulsifiable or solubleconcentrates most frequently comprise about 5 to about 80% by weight ofthe active ingredient, while the emulsions or solutions which are readyfor application contain, in their case, about 0.01 to about 20% of theactive ingredient. Besides the solvent, the emulsifiable or solubleconcentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilizers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, for example, to plants, may be obtained from theseconcentrates by dilution with water. These compositions are includedwithin the scope of the compositions which may be employed in thepresent invention. The emulsions may be in the form of water-in-oil oroil-in-water type and they may have a thick consistency.

The liquid compositions of this invention may, in addition to normalagricultural use applications be used for example to treat substrates orsites infested or liable to infestation by arthropods (or other pestscontrolled by compounds of this invention) including premises, outdooror indoor storage or processing areas, containers or equipment orstanding or running water.

All these aqueous dispersions or emulsions or spraying mixtures can beapplied, for example, to crops by any suitable means, chiefly byspraying, at rates which are generally of the order of about 100 toabout 1,200 liters of spraying mixture per hectare, but may be higher orlower (eg. low or ultra-low volume) depending upon the need orapplication technique. The compounds or compositions according to theinvention are conveniently applied to vegetation and in particular toroots or leaves having pests to be eliminated. Another method ofapplication of the compounds or compositions according to the inventionis by chemigation, that is to say, the addition of a formulationcontaining the active ingredient to irrigation water. This irrigationmay be sprinkler irrigation for foliar pesticides or it can be groundirrigation or underground irrigation for soil or for systemicpesticides.

The concentrated suspensions, which can be applied by spraying, areprepared so as to produce a stable fluid product which does not settle(fine grinding) and usually contain from about 10 to about 75% by weightof active ingredient, from about 0.5 to about 30% of surface-activeagents, from about 0.1 to about 10% of thixotropic agents, from about 0to about 30% of suitable additives, such as anti-foaming agents,corrosion inhibitors, stabilizers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble. Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

The wettable powders (or powders for spraying) are usually prepared sothat they contain from about 10 to about 80% by weight of activeingredient, from about 20 to about 90% of a solid carrier, from about 0to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilizers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient(s) is(are) thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is(are) ground using a mill or other suitablegrinder. This produces wettable powders, the wettability and thesuspendability of which are advantageous. They may be suspended in waterto give any desired concentration and this suspension can be employedvery advantageously in particular for application to plant foliage.

The "water dispersible granules (WG)" (granules which are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. from about 1 to about 20% by weight, or with anaqueous solution of a dispersing agent or binder, followed by drying andscreening), or by a dry route (compacting followed by grinding andscreening).

The rates and concentrations of the formulated compositions may varyaccording to the method of application or the nature of the compositionsor use thereof. Generally speaking, the compositions for application tocontrol arthropod, plant nematode, helminth or protozoan pests usuallycontain from about 0.00001% to about 95%, more particularly from about0.0005% to about 50% by weight of one or more compounds of formula (I),or pesticidally acceptable salts thereof, or of total active ingredients(that is to say the compound of formula (I), or a pesticidallyacceptable salt thereof, together with: other substances toxic toarthropods or plant nematodes, anthelmintics, anticoccidials,synergists, trace elements or stabilizers). The actual compositionsemployed and their rate of application will be selected to achieve thedesired effect(s) by the farmer, livestock producer, medical orveterinary practitioner, pest control operator or other person skilledin the art.

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more compounds of formula (I) or pesticidallyacceptable salts thereof. For administration to animals orally orparenterally, including percutaneously, solid or liquid compositions,these normally contain from about 0.1% to about 90% by weight of one ormore compounds of formula (I) or pesticidally acceptable salts thereof.Medicated feedstuffs normally contain from about 0.001% to about 3% byweight of one or more compounds of formula (I) or pesticidallyacceptable salts thereof. Concentrates or supplements for mixing withfeedstuffs normally contain from about 5% to about 90%, preferably fromabout 5% to about 50%, by weight of one or more compounds of formula (I)or pesticidally acceptable salts thereof. Mineral salt licks normallycontain from about 0.1% to about 10% by weight of one or more compoundsof formula (I) or pesticidally acceptable salts thereof.

Dusts or liquid compositions for application to livestock, goods,premises or outdoor areas may contain from about 0.0001% to about 15%,more especially from about 0.005% to about 2.0%, by weight, of one ormore compounds of formula (I) or pesticidally acceptable salts thereof.Suitable concentrations in treated waters are between about 0.0001 ppmand about 20 ppm, more particularly about 0.001 ppm to about 5.0 ppm ofone or more compounds of formula (I), or pesticidally acceptable saltsthereof, and may be used therapeutically in fish farming withappropriate exposure times. Edible baits may contain from about 0.01% toabout 5%, preferably from about 0.01% to about 1.0%, by weight, of oneor more compounds of formula (I) or pesticidally acceptable saltsthereof.

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of compounds of formula (I), or pesticidallyacceptable salts thereof, will depend upon the species, age, or healthof the vertebrate and upon the nature and degree of its actual orpotential infestation by arthropod, helminth or protozoan pests. Asingle dose of about 0.1 to about 100 mg, preferably about 2.0 to about20.0 mg, per kg body weight of the animal or doses of about 0.01 toabout 20.0 mg, preferably about 0.1 to about 5.0 mg, per kg body weightof the animal per day, for sustained medication, are generally suitableby oral or parenteral administration. By use of sustained releaseformulations or devices, the daily doses required over a period ofmonths may be combined and administered to animals on a single occasion.

The following composition EXAMPLES 2A-2M illustrate compositions for useagainst arthropods, especially mites or insects, plant nematodes, orhelminth or protozoan pests which comprise, as active ingredient,compounds of formula (I), or pesticidally acceptable salts thereof, suchas those described in the preparative examples. The compositionsdescribed in EXAMPLES 2A-2M can each be diluted to give a sprayablecomposition at concentrations suitable for use in the field. Genericchemical descriptions of the ingredients (for which all of the followingpercentages are in weight percent), used in the composition EXAMPLES2A-2M exemplified below, are as follows:

    ______________________________________                                        Trade Name                                                                              Chemical Description                                                ______________________________________                                        Ethylan BCP                                                                             Nonylphenol ethylene oxide condensate                                 Soprophor BSU Tristyrylphenol ethylene oxide condensate                       Arylan CA A 70% w/v solution of calcium dodecylbenzenesulfon-                  ate                                                                          Solvesso 150 Light C.sub.10 aromatic solvent                                  Arylan S Sodium dodecylbenzenesulfonate                                       Darvan No 2 Sodium lignosulphonate                                            Celite PF Synthetic magnesium silicate carrier                                Sopropon T36 Sodium salts of polycarboxylic acids                             Rhodigel 23 Polysaccharide xanthan gum                                        Bentone 38 Organic derivative of magnesium montmorillonite                    Aerosil Microfine silicon dioxide                                           ______________________________________                                    

EXAMPLE 2A

A water soluble concentrate is prepared with the composition as follows:

    ______________________________________                                        Active ingredient  7%                                                           Ethylan BCP 10%                                                               N-methylpyrrolidone 83%                                                     ______________________________________                                    

To a solution of Ethylan BCP dissolved in a portion ofN-methylpyrrolidone is added the active ingredient with heating andstirring until dissolved. The resulting solution is made up to volumewith the remainder of the solvent.

EXAMPLE 2B

An emulsifiable concentrate (EC) is prepared with the composition asfollows:

    ______________________________________                                        Active ingredient                                                                              25% (max)                                                      Soprophor BSU 10%                                                             Arylan CA  5%                                                                 N-methylpyrrolidone 50%                                                       Solvesso 150 10%                                                            ______________________________________                                    

The first three components are dissolved in N-methylpyrrolidone and tothis is then added the Solvesso 150 to give the final volume.

EXAMPLE 2C

A wettable powder (WP) is prepared with the composition as follows:

    ______________________________________                                               Active ingredient                                                                       40%                                                            Arylan S  2%                                                                  Darvan No 2  5%                                                               Celite PF 52%                                                               ______________________________________                                    

The ingredients are mixed and ground in a hammer-mill to a powder with aparticle size of less than 50 microns.

EXAMPLE 2D

An aqueous-flowable formulation is prepared with the composition asfollows:

    ______________________________________                                        Active ingredient                                                                             40.00%                                                          Ethylan BCP 1.00%                                                             Sopropon T360 0.20%                                                           Ethylene glycol 5.00%                                                         Rhodigel 230 0.15%                                                            Water 53.65%                                                                ______________________________________                                    

The ingredients are intimately mixed and are ground in a bead mill untila mean particle size of less than 3 microns is obtained.

EXAMPLE 2E

An emulsifiable suspension concentrate is prepared with the compositionas follows:

    ______________________________________                                        Active ingredient                                                                             30.0%                                                           Ethylan BCP 10.0%                                                             Bentone 38  0.5%                                                              Solvesso 150 59.5%                                                          ______________________________________                                    

The ingredients are intimately mixed and ground in a beadmill until amean particle size of less than 3 microns is obtained.

EXAMPLE 2F

A water dispersible granule is prepared with the composition as follows:

    ______________________________________                                               Active ingredient                                                                       30%                                                            Darvan No 2 15%                                                               Arylan S  8%                                                                  Celite PF 47%                                                               ______________________________________                                    

The ingredients are mixed, micronized in a fluid-energy mill and thengranulated in a rotating pelletizer by spraying with water (up to 10%).The resulting granules are dried in a fluid-bed drier to remove excesswater.

EXAMPLE 2G

A dusting powder is prepared with the composition as follows:

    ______________________________________                                        Active ingredient                                                                               1 to 10%                                                      Talc powder-superfine 99 to 90%                                             ______________________________________                                    

The ingredients are intimately mixed and further ground as necessary toachieve a fine powder. This powder may be applied to a locus ofarthropod infestation, for example refuse dumps, stored products orhousehold goods or animals infested by, or at risk of infestation by,arthropods to control the arthropods by oral ingestion. Suitable meansfor distributing the dusting powder to the locus of arthropodinfestation include mechanical blowers, handshakers or livestock selftreatment devices.

EXAMPLE 2H

An edible bait is prepared with the composition as follows:

    ______________________________________                                        Active ingredient                                                                              0.1 to 1.0%                                                    Wheat flour 80%                                                               Molasses 19.9 to 19%                                                        ______________________________________                                    

The ingredients are intimately mixed and formed as required into a baitform. This edible bait may be distributed at a locus, for exampledomestic or industrial premises, e.g. kitchens, hospitals or stores, oroutdoor areas, infested by arthropods, for example ants, locusts,cockroaches or flies, to control the arthropods by oral ingestion.

EXAMPLE 2I

A solution formulation is prepared with a composition as follows:

    ______________________________________                                        Active ingredient                                                                              15%                                                            Dimethyl sulfoxide 85%                                                      ______________________________________                                    

The active ingredient is dissolved in dimethyl sulfoxide with mixingand/or heating as required. This solution may be applied percutaneouslyas a pour-on application to domestic animals infested by arthropods or,after sterilization by filtration through a polytetrafluoroethylenemembrane (0.22 micrometer pore size), by parenteral injection, at a rateof application of from 1.2 to 12 ml of solution per 100 kg of animalbody weight.

EXAMPLE 2J

A wettable powder is prepared with the composition as follows:

    ______________________________________                                               Active ingredient                                                                       50%                                                            Ethylan BCP  5%                                                               Aerosil  5%                                                                   Celite PF 40%                                                               ______________________________________                                    

The Ethylan BCP is absorbed onto the Aerosil which is then mixed withthe other ingredients and ground in a hammer-mill to give a wettablepowder, which may be diluted with water to a concentration of from0.001% to 2% by weight of the active compound and applied to a locus ofinfestation by arthropods, for example, dipterous larvae or plantnematodes, by spraying, or to domestic animals infested by, or at riskof infection by arthropods, helminths or protozoa, by spraying ordipping, or by oral administration in drinking water, to control thearthropods, helminths or protozoa.

EXAMPLE 2K

A slow release bolus composition is formed from granules containing thefollowing components in varying percentages (similar to those describedfor the previous compositions) depending upon need:

    ______________________________________                                                   Active ingredient                                                    Density agent                                                                 Slow-release agent                                                            Binder                                                                      ______________________________________                                    

The intimately mixed ingredients are formed into granules which arecompressed into a bolus with a specific gravity of 2 or more. This canbe administered orally to ruminant domestic animals for retention withinthe reticulorumen to give a continual slow release of active compoundover an extended period of time to control infestation of the ruminantdomestic animals by arthropods, helminths or protozoa.

EXAMPLE 2L

A slow release composition in the form of granules, pellets, brickettesor the like can be prepared with compositions as follows:

    ______________________________________                                        Active ingredient  0.5 to 25%                                                   Polyvinyl chloride 75 to 99.5%                                                Dioctyl phthalate (plasticizer)                                             ______________________________________                                    

The components are blended and then formed into suitable shapes bymelt-extrusion or molding. These composition are useful, for example,for addition to standing water or for fabrication into collars oreartags for attachment to domestic animals to control pests by slowrelease.

EXAMPLE 2M

A water dispersible granule is prepared with the composition as follows:

    ______________________________________                                        Active ingredient                                                                              85% (max)                                                      Polyvinylpyrrolidone 5%                                                       Attapulgite clay 6%                                                           Sodium lauryl sulfate 2%                                                      Glycerine 2%                                                                ______________________________________                                    

The ingredients are mixed as a 45% slurry with water and wet milled to aparticle size of 4 microns, then spray-dried to remove water.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions and changes can be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What we claim is:
 1. A compound having the formula: ##STR10## or apesticidally acceptable salt thereof, wherein: R₃₁ and R₃₂, which arethe same or different, are each OCH₃, OC₂ H₅, S(O)_(m) CH₃ or S(O)_(n)C₂ H₅ ; or R₃₁ and R₃₂ are combined to form OCH₂ CH₂ O, O(CH₂)₃ O,S(CH₂)₂ S, S(O)(CH₂)₂ S, S(O)(CH₂)₂ S(O), S(O)₂ (CH₂)₂ S(O), S(O)₂(CH₂)₂ S(O)₂, S(CH₂)₂ O, S(O)(CH₂)₂ O, S(O)₂ (CH₂)₂ O, O(CH₂)[CH(CH₂OH]O, O(CH₂)[C(CH₂ OH)(CH₂ OH)]O, OCH(COOCH₃)CH(COOCH₃)O, OCH(COOC₂H₅)CH(COOC₂ H₅)O, OCH₂ C(COOCH₃)(COOCH₃)CH₂ O, OCH₂ C(COOC₂ H₅)(COOC₂H₅)CH₂ O, OCH₂ CH(CH₃)O, SCH₂ CH₂ NH, OCH₂ CH(CH₂ CH₂ OH)O, OCH₂ C(CH₂OH)₂ CH₂ O, OCH₂ CH(CH₂ SCH₃)O or OCH₂ CH(CH₂ SOCH₃)O;R₄ is R₂₆ ;S(O)_(d) R₂₆ ; or S(═R₂₇)(═NR₂₈)R₂₆ ; R₂₆ is C₁ -C₆ alkyl, optionallysubstituted with one or more halogen which are the same or different; R₅is NH₂ or C₁ -C₆ alkylamino wherein the alkyl portion optionally bearsone or more substituents selected from the group consisting of NO₂,halogen, CN, (C₁ -C₆ alkoxy)carbonyl, OH, C₁ -C₆ alkoxy, C₁ -C₆alkylthio, C₁ -C₆ alkylsulfinyl, C₁ -C₆ alkylsulfonyl and carbamoyl; R₂₇is NR₂₈, O or a lone pair of electrons; R₂₈ is H; C₁ -C₆ alkyl; C₁ -C₆haloalkyl; COR₂₄ ; S(O)_(e) R₂₄ ; COOR₂₄ ; C(O)N(R₂₀)(R₂₁); C(O)SR₂₄ ;C(S)OR₂₄ ; SO₂ NR₂₀ R₂₁ ; P(O)_(q) (R₂₀)(R₂₁); P(O)_(q) (OR₂₀)(OR₂₁);C(═NR₂₀)NR₂₀ R₂₁ ; C(═NR₂₀)(OR₂₁); C(S)N(R₂₀)(R₂₁); C(O)C(O)R₂₀ ;C(O)C(O)OR₂₀ ; C(O)C(O)NR₂₀ R₂₁ ; or C(O)NR₂₀ SO₂ R₂₁ ; q is 0 or 1; R₂₀and R₂₁, which are the same or different, are each H, C₁ -C₆ alkyl,benzyl, allyl, propargyl, or C₆ -C₁₀ aryl optionally bearing one or moresubstituents selected from the group consisting of halogen, C₁ -C₆alkyl, C₁ -C₆ alkoxy, CN, NO₂, C₁ -C₆ haloalkyl and C₁ -C₆ haloalkoxy;R₂₄ is C₁ -C₆ alkyl, optionally bearing one or more substituentsselected from the group consisting of NO₂, CN, halogen, C₁ -C₆ alkoxy,amino, (C₁ -C₆ alkoxy)carbonyl and OH; Z is C--R₁₆ ; R₁₂, R₁₃, R₁₄, R₁₅and R₁₆, which are the same or different, are each H; halogen; SF₅ ; CN;NO₂ ; R₂₅ ; S(O)_(f) R₂₅ ; OH; OR₂₅ ; N(R₃₆)(R₃₇); CON(R₂₅)(R₃₇); or N₃(azido); R₃₆ and R₃₇, which are the same or different, are each H or C₁-C₆ alkyl; R₂₅ is C₁ -C₆ alkyl, optionally substituted with one or morehalogen which are the same or different; and R₃₃ is C₁ to C₃ alkyl,optionally bearing one or more substituents selected from the groupconsisting of halogen, NO₂, C₁ -C₆ alkoxy, CN, COOH, COO(C₁ -C₆ alkyl),and C(O)NH₂ ; and n, d, e and f, which are the same or different, areeach 0, 1 or
 2. 2. A compound according to claim 1, wherein R₁₃ and R₁₅,which are the same or different, are each H or halogen.
 3. A compoundaccording to claim 1, wherein R₁₂ is halogen.
 4. A compound according toclaim 1, wherein R₁₆ is H or halogen.
 5. A compound according to claim1, wherein R₁₄ is halogen, SF₅, R₂₅, S(O)_(f) R₂₅ or OR₂₅.
 6. A compoundaccording to claim 1, wherein R₁₂ is chlorine, R₁₃ and R₁₅ are each H,R₁₄ is CF₃ and Z is C--Cl.
 7. A compound according to claim 1, whereinR₁₃ and R₁₅, which are the same or different, are each H or halogen; R₁₂is halogen; R₁₆ is H or halogen; and R₁₄ is halogen, SF₅, R₂₅, S(O)_(f)R₂₅ or OR₂₅.
 8. A compound according to claim 1, wherein R₄ is S(O)_(d)R₂₆.
 9. A compound according to claim 1, wherein R₂₆ is CH₃ or CH₂ CH₃.10. A compound according to claim 1, wherein R₁₃ and R₁₅ are H.
 11. Acompound according to claim 1, wherein R₁₄ is CF₃, OCF₃ or SF₅.
 12. Acompound according to claim 1, wherein R₃₃ is CH₃.
 13. A compoundaccording to claim 1, wherein R₂₆ is CH₃ or CH₂ CH₃ ; R₁₃ and R₁₅ areeach H; R₁₂ is halogen; R₁₆ is H or halogen; R₁₄ is CF₃, OCF₃ or SF₅ ;and R₃₃ is CH₃.
 14. A compound according to claim 1, wherein R₄ isS(O)_(d) CH₃, R₅ is NH₂, R₁₂ is Cl, R₁₃ is H, R₁₄ is CF₃, R₁₅ is H, Z isC--Cl and R₃₃ is CH₃.
 15. A compound according to claim 1, wherein R₃₁and R₃₂, which are the same or different, are each OCH₃, OC₂ H₅, SCH₃ orSC₂ H₅.
 16. A compound according to claim 1, wherein R₃₁ and R₃₂ areeach OCH₃.
 17. A compound according to claim 14, wherein R₃₁ and R₃₂ areeach OCH₃.
 18. A compound according to claim 1, wherein R₃₁ and R₃₂ arecombined to form OCH₂ CH₂ O, O(CH₂)₃ O, S(CH₂)₂ S, S(O)(CH₂)₂ S,S(O)(CH₂)₂ S(O), S(O)₂ (CH₂)₂ S(O), S(O)₂ (CH₂)₂ S(O)₂, S(CH₂)₂ O,S(O)(CH₂)₂ O, S(O)₂ (CH₂)₂ O, O(CH₂)[CH(CH₂ OH)]O, O(CH₂)[C(CH₂ OH)(CH₂OH)]O, OCH(COOCH₃)CH(COOCH₃)O, OCH(COOC₂ H₅)CH(COOC₂ H₅)O, OCH₂C(COOCH₃)(COOCH₃)CH₂ O, OCH₂ C(COOC₂ H₅)(COOC₂ H₅)CH₂ O, OCH₂ CH(CH₃)O,SCH₂ CH₂ NH, OCH₂ CH(CH₂ CH₂ OH)O, OCH₂ C(CH₂ OH)₂ CH₂ O, OCH₂ CH(CH₂SCH₃)O or OCH₂ CH(CH₂ SOCH₃)O.
 19. A compound according to claim 14,wherein R₃₁ and R₃₂ are combined to form OCH₂ CH₂ O, O(CH₂)₃ O, S(CH₂)₂S, S(O)(CH₂)₂ S, S(O)(CH₂)₂ S(O), S(O)₂ (CH₂)₂ S(O), S(O)₂ (CH₂)₂ S(O)₂,S(CH₂)O, S(O)(CH₂)₂ O, S(O)₂ (CH₂)₂ O, O(CH₂)[CH(CH₂ OH)]O, O(CH₂)[C(CH₂OH)(CH₂ OH)]O, OCH(COOCH₃)CH(COOCH₃)O, OCH(COOC₂ H₅)CH(COOC₂ H₅)O, OCH₂C(COOCH₃)(COOCH₃)CH₂ O, OCH₂ C(COOC₂ H₅)(COOC₂ H₅)CH₂ O, OCH₂ CH(CH₃)O,SCH₂ CH₂ NH, OCH₂ CH(CH₂ CH₂ OH)O, OCH₂ C(CH₂ OH)₂ CH₂ O, OCH₂ CH(CH₂SCH₃)O or OCH₂ CH(CH₂ SOCH₃)O.
 20. A compound according to claim 1,wherein R₃₁ and R₃₂, which are the same or different, are each OCH₃, OC₂H₅, SCH₃ or SC₂ H₅ ; or R₃₁ and R₃₂ are combined to form OCH₂ CH₂ O,O(CH₂)₃ O, S(CH₂)₂ S, S(O)(CH₂)₂ S, S(O)(CH₂)₂ S(O), S(O)₂ (CH₂)₂ S(O),S(O)₂ (CH₂)₂ S(O)₂, S(CH₂)₂ O, S(O)(CH₂)₂ O, S(O)₂ (CH₂)₂ O,O(CH₂)[CH(CH₂ OH)]O, O(CH₂)[C(CH₂ OH)(CH₂ OH)]O, OCH(COOCH₃)CH(COOCH₃)O,OCH(COOC₂ H₅)CH(COOC₂ H₅)O, OCH₂ C(COOCH₃)(COOCH₃)CH₂ O, OCH₂ C(COOC₂H₅)(COOC₂ H₅)CH₂ O, OCH₂ CH(CH₃)O, SCH₂ CH₂ NH, OCH₂ CH(CH₂ CH₂ OH)O,OCH₂ C(CH₂ OH)₂ CH₂ O, OCH₂ CH(CH₂ SCH₃)O or OCH₂ CH(CH₂ SOCH₃)O; R₄ isS(O)_(d) R₂₆ ; R₂₆ is CH₃ or CH₂ CH₃ ; R₁₃ and R₁₅ are each H; R₁₂ ishalogen; R₁₆ is H or halogen; R₁₄ is CF₃, OCF₃ or SF₅ ; and R₃₃ is CH₃.21. The compound according to claim 1, having the formula: ##STR11##wherein: (a) R₃₁ is OCH₃, R₃₂ is OCH₃ and d is O; or(b) R₃₁ is OCH₃, R₃₂is OCH₃ and d is
 1. 22. The compound according to claim 1, having theformula: ##STR12## wherein: (a) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is H and d is0;(b) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₃ and d is 0; (c) R₃₁₀ is O, R₃₂₀is O, R₁₇ is H and d is 2; (d) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₂ OH and dis 0; (e) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₂ OH and d is 2; (f) R₃₁₀ is O,R₃₂₀ is O, R₁₇ is CH₃ and d is 2; (g) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is H andd is 1; (h) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₃ and d is 1; (i) R₃₁₀ is S,R₃₂₀ is NH, R₁₇ is H and d is 1; (j) R₃₁₀ is S, R₃₂₀ is S, R₁₇ is H andd is 0; or (k) R₃₁₀ is S, R₃₂₀ is S, R₁₇ is H and d is
 2. 23. Thecompound according to claim 1, having the formula: ##STR13## wherein:(a) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is H, R₁₈ is H and d is 0;(b) R₃₁₀ is O,R₃₂₀ is O, R₁₇ is H, R₁₈ is H and d is 2; or (c) R₃₁₀ is O, R₃₂₀ is O,R₁₇ is CH₂ OH, R₁₈ is CH₂ OH and d is
 0. 24. The compound according toclaim 1, having the formula: ##STR14## wherein: (a) R₃₁₀ is S, R₃₂₀ isS, R₁₇ is H and d is 1;(b) R₃₁₀ is SO, R₃₂₀ is S, R₁₇ is H and d is 0;(c) R₃₁₀ is SO, R₃₂₀ is S, R₁₇ is H and d is 1; (d) R₃₁₀ is SO, R₃₂₀ isS, R₁₇ is H and d is 2; (e) R₃₁₀ is SO, R₃₂₀ is SO, R₁₇ is H and d is 2;(f) R₃₁₀ is S, R₃₂₀ is O, R₁₇ is H and d is 2; (g) R₃₁₀ is S, R₃₂₀ is O,R₁₇ is H and d is 0; (h) R₃₁₀ is SO₂, R₃₂₀ is SO₂, R₁₇ is H and d is 2;(i) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₂ OH and d is 1; (j) R₃₁₀ is O, R₃₂₀is O, R₁₇ is CH₂ SCH₃ and d is 0; (k) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₂SOCH₃ and d is 0; (l) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₂ SOCH₃ and d is 1;(m) R₃₁₀ is O, R₃₂₀ is O, R₁₇ is CH₂ SCH₃ and d is 2; or (n) R₃₁₀ is O,R₃₂₀ is O, R₁₇ is CH₂ SOCH₃ and d is
 2. 25. The compound according toclaim 1, having the formula: ##STR15## wherein: (a) R₅ is NHCH₂ CH₃ andd is 2;(b) R₅ is NHCH₃ and d is 2; (c) R₅ is NHCH₂ CH₃ and d is 0; (d)R₅ is NHCH₂ CH₃ and d is 1; (e) R₅ is NHCH₃ and d is 0; or (f) R₅ isNHCH₃ and d is
 1. 26. A pesticidal composition comprising a pesticidallyeffective amount of a compound of formula (I) as claimed in claim 1, ora pesticidally acceptable salt thereof, and a pesticidally acceptablediluent or carrier therefor.
 27. A pesticidal composition according toclaim 26, comprising from about 0.05% to about 95% by weight of acompound of formula (I).
 28. An insecticidal composition comprising aninsecticidally effective amount of a compound of formula (I) as claimedin claim 1, or an insecticidally acceptable salt thereof, and aninsecticidally acceptable diluent or carrier therefor.
 29. A method ofcontrolling pests at a locus which comprises applying to said locus apesticidally effective amount of a compound as claimed in claim 1, or apesticidally acceptable salt thereof.
 30. A method according to claim29, wherein the pests are insects and an insecticidally effective amountof the compound of formula (I) is applied.
 31. A method according toclaim 30, wherein the insects are sucking insects.
 32. A methodaccording to claim 29, wherein the locus is an area used or to be usedfor the growing of crops.
 33. A method according to claim 37, whereinthe compound of formula (I) is applied at a rate of from about 5 g toabout 1 kg/ha.
 34. A method according to claim 29, wherein the locus isan animal.
 35. A method according to claim 34, wherein the compound offormula (I) is applied at a rate of from about 0.1 to about 20 mg per kgbody weight of animal per day.
 36. A process for the preparation of acompound of formula (I) as claimed in claim 1, said process comprisingreacting a compound having the formula ##STR16## wherein R₄, R₅, R₁₂,R₁₃, R₁₄, R₁₅, Z and R₃₃ are as defined in claim 1 and R₃₄ is oxygen orsulfur, with an alcohol having the formula CH₃ OH or C₂ H₅ OH, a thiolhaving the formula CH₃ SH or C₂ H₅ SH, or a compound having the formulaHOCH₂ CH₂ OH, HO(CH₂)₃ OH, HS(CH₂)₂ SH, HS(CH₂)₂ OH, HOCH₂ [CH(CH₂OH)]OH, HOCH₂ [C(CH₂ OH)(CH₂ OH)]OH, HOCH(COOCH₃)CH(COOCH₃)OH,HOCH(COOC₂ H₅)CH(COOC₂ H₅)OH, HOCH₂ C(COOCH₃)(COOCH₃)CH₂ OH, HOCH₂CH(COOC₂ H₅)(COOC₂ H₅)CH₂ OH, HOCH₂ CH(CH₃)OH, HSCH₂ CH₂ NH₂, HOCH₂CH(CH₂ CH₂ OH)OH, HOCH₂ C(CH₂ OH)₂ CH₂ OH or HOCH₂ CH(CH₂SCH₃)OH;followed by, if desired, oxidation of a resultant compound offormula (I) having one or two thio groups to the corresponding compoundof formula (I) having one or two sulfinyl or sulfonyl groups.